JPH10195302A - Heat-resistant resin composition and molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which can give a molded product excellent in heat resistance, water repellency and oil repellency by mixing a thermoplastic heat-resistant resin having a specified or higher molding temperature with a polymer obtained by polymerizing a component consisting essentially of fluoroalkyl α-fluoroacrylate. SOLUTION: This composition comprises a thermoplastic heat-resistant resin having a molding temperature of 300 deg.C or above (e.g. polyphenylene sulfide) and a polymer obtained by polymerizing a component consisting essentially of fluoroalkyl α-fluoroacrylate represented by formula I [wherein Rf is X- RF-(CH2 )n - or a group of formula II; n is 0 or 1; X is H, F or CH3 ; RF is a 1-20C perfluoroalkylene, provided that it is -C(CF3 )2 - when n=0; Z is F or CF3 ; R'F is a 1-3C perfluoroalkyl; a to e are each 0 or 1 or greater; the sum of a to e is 1 or greater; and the order of bonding of the respective types of repeating units in parentheses with subscripts a to e is not limited]. This composition can give a molded product which has persistent water/oil repellency owing to the surface segregation of the polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant resin composition and a molded article, and more particularly to a resin molded article used in electronic equipment and industrial fields requiring heat resistance, and a resin composition suitable therefor. About.

[0002]

2. Description of the Related Art A heat-resistant resin called a super engineering plastic having a molding temperature as high as 300 ° C. or higher has been used for various purposes in recent years. Representative examples of such high heat-resistant resin, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, polyamide imide, polyether imide, polyimides such as thermoplastic polyimide, polyether ketone, polyether ether ketone and the like Examples thereof include polyketones and wholly aromatic polyesters. Since these resins have excellent mechanical properties, they are used as various structural materials instead of metals. However, these resins are often required to have sliding properties, antifouling properties, and non-adhesive properties in actual use. Modification of the surface of these resin moldings with a fluorine-based organic material is performed. ing.

Conventionally, such resin surface modification has been carried out by coating or using a solution or dispersion of a fluoropolymer or a low molecular fluorine compound having a functional group, or by directly melting the fluoropolymer or low molecular fluorine compound. A technique such as kneading (internal addition method) has been used. As a coating method, an example of a separating claw for a copying machine in which a dispersion of a copolymer of tetrafluoroethylene (TFE) and perfluoroalkyl vinyl ether (PFA) is applied to a polyimide molded article and baked to prevent toner adhesion ( Japanese Patent Publication No. 7-86726) and an example using a solution of a low-molecular fluorine compound having a functional group for the same use of the separation nail (Japanese Patent Publication No. 6-58581). On the other hand, in the internal addition method, low-molecular-weight polytetrafluoroethylene (PTF
E) There are many examples of blending a small amount of powder with a resin (U.S. Pat. No. 3,487,454; Japanese Patent Application Laid-Open No. 58-160353).
And Japanese Patent Publication No. 63-1989). In addition, a method is known in which a polyolefin-based resin is mixed with a polyfluoroalkyl group-containing polyacrylate and polymethacrylate to obtain a molded article having water / oil repellency (JP-A-3-7745 and JP-A-3-41162). ing.

[0004] However, the modification by coating has the expected effect at first, but since the surface may peel off as time passes, the molded body is often physically and / or chemically treated before painting. Processing needs to be performed. Such pretreatment and painting steps increase processing costs. In this regard, the kneading method is superior in processing cost, but has some problems. One is that the fluorine-based material is mixed in the whole molded body, so that the surface modification effect must be achieved by using more fluorine-based material than by the coating method, which increases the material cost. . Further, even if the content of the fluorine-based material is increased, it is extremely difficult to form a surface of only the fluorine-based material like a coating, and it is difficult to obtain a sufficient effect. In order to melt and knead a small amount of fluorine-based material and obtain a sufficient surface modification effect, it is required that the fluorine-based material be easily collected on the surface of the molded body during molding. In order to cause such surface segregation, it is important to select a fluorine-based material. Commonly used internal fluorine-based materials include PTFE, PFA,
Copolymer of TFE and hexafluoropropane (FE
P), a copolymer containing ethylene and TFE as main components (ET
Although there are resins such as FE), they are unlikely to segregate on the surface of the molded article and cannot exert a sufficient effect unless added in a large amount. On the other hand, Japanese Patent Application Laid-Open Nos. Hei 3-7745 and Hei 3
Polymers having a perfluoroalkyl group side chain in the molecule, such as polyacrylic acid or perfluoroalkyl methacrylate having a perfluoroalkyl group in the side chain disclosed in the publication such as JP-41162, have side chains on the surface. It is a material that is easily oriented. However, the above-mentioned molding temperature is 3
As for the surface modification of a heat-resistant resin having a temperature as high as 00 ° C. or higher, there is no material known to cause surface segregation by the internal addition method. Perfluoroalkyl poly (meth) acrylate has insufficient heat resistance during melt kneading.

[0005]

As described above, the surface modification of a heat-resistant resin having a molding temperature of 300 ° C. or higher cannot be effectively performed by the conventional method. An object of the present invention is to provide a heat-resistant resin composition capable of effectively modifying the surface of such a heat-resistant resin, and a surface-modified heat-resistant resin molded article.

[0006]

In order to solve the above-mentioned problems, the present invention provides a thermoplastic heat-resistant resin (A) having a molding temperature of 300 ° C. or more, and formula (1):

## STR1 Rf-O-CO-CF = CH 2 (1) { wherein, Rf _{is, X-R F - (CH} 2) n -, or the formula (2):

Embedded image R _F ′-(OCF ₂ CF ₂ CF ₂ ) a- (OCF (C
F ₃ ) CF ₂ ) b- (OCF ₂ ) c- (OCF ₂ CF ₂ ) d-OC (Z)
F- (CF ₂ ) e- (where n is 1 or 0; X represents hydrogen or a fluorine atom or a methyl group; R _F has 1 to 2 carbon atoms)
It is a linear or branched perfluoroalkylene group of 0. However, when n is 0 R _F is -C (CF _{3) 2} - shows a. Z represents a fluorine atom or a trifluoromethyl group, and R _F ′ represents a perfluoroalkyl group having 1 to 3 carbon atoms. a, b, c, d and e each independently represent an integer of 0 or 1 or more, a + b + c + d + e is at least 1, and each repetition of a, b, c, d and e The order of the units is not limited in the formula. ). The present invention provides a resin composition comprising a polymer (B) obtained by polymerizing α-fluoroacrylic acid represented by｝ as an essential component, and a resin molded article produced from this resin composition.

As the thermoplastic resin (A) having a molding temperature of 300 ° C. or higher, a resin generally called super engineering plastic can be used, and typically, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate , Polyamide imide, polyether imide,
Examples thereof include polyether ether ketone, polyimide, polyether nitrile, and aromatic polyester. These may be used alone or as a blend of two or more.

As the α-fluoroacrylic acid fluoroacrylic used in the present invention, those having a heat resistance of at least 300 ° C. are particularly preferred. As an example, CH ₂ = CFCOOC (C
F ₃ ) ₂ H, CH ₂ ＣＦCFCOOCH ₂ C (CF ₃ ) ₂ CH ₃ , C
H ₂ = CFCOOCH ₂ CF ₃ , CH ₂ = CFCOOCH _{2
CF 2 CF 2 H, CH 2} = CFCOOCH 2 CF 2 CF 3,
CH ₂ = CFCOOCH ₂ CF ₂ CF ₂ CF ₃ , CH ₂ = CF
COOCH ₂ (CF ₂ ) ₄ H, CH ₂ ＣＦCFCOOCH ₂ (CF
₂ ) ₄ F, CH ₂ ＣＦCFCOOCH ₂ (CF ₂ ) ₇ F, CH ₂ ＣC
FCOOCH ₂ (CF ₂ ) ₈ H, CH ₂ ＣＦCFCOOCH ₂ (C
F ₂ ) ₈ F, CH ₂ ＣＦCFCOOCH ₂ (CF ₂ ) ₉ F, CH ₂ =
CFCOOCH ₂ (CF ₂ ) ₁₁ F, CH ₂ ＣＦCFCOOCH ₂
—CF (CF ₃ ) OCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₃ .

The polymer (B) is a homopolymer or a copolymer of the above-mentioned α-fluoroacrylic acid acrylate, or a copolymer of α-fluoroacrylic acid and another monomer copolymerizable therewith. .

Examples of monomers copolymerizable with α-fluoroacrylic acid fluoroacrylic acid include derivatives of methacrylic acid or acrylic acid, such as fluorine-based or non-fluorine-based esters, amides and acid halides, and α-fluoroacrylates. Derivatives such as non-fluorinated esters of acrylic acid, amides, and acid halides are exemplified.

The proportion of α-fluoroacrylic acid in the polymer (B) is not particularly limited as long as the heat resistance is not reduced. A preferred ratio is 50-100% by weight based on the weight of the polymer (B).

The weight average molecular weight of the polymer (B) (determined by gel permeation chromatography) is 100
0-4,000,000, preferably 10,000.
It is in the range of 0-1,000,000. If the molecular weight is too small, bleed-out tends to occur. If the molecular weight is too large, fluidity is reduced and surface orientation becomes difficult.

The alcohol-derived portion of the α-fluoroacrylic acid of the polymer (B) preferably has a longer carbon number from the viewpoint of water and oil repellency, but the effect is shorter. The ratio of the resin composition polymer (B) is preferably 1 to 20% by weight based on the weight of the resin composition. If the amount is less than the lower limit, the effect of addition is low.

In order to obtain the resin composition of the present invention, for example,
The components may be blended using a conventional kneader / mixer such as a single-screw extruder, a twin-screw extruder, an open roll, a kneader, and a mixer, but are not limited thereto.

The resin composition of the present invention may further contain an existing fluorine resin for internal addition. The addition of the fluororesin is effective for further improving the sliding characteristics and the non-adhesiveness. The amount of the fluororesin is 5 to 5 parts by weight of the resin composition.
40% by weight is preferred. If the amount is too large, the moldability decreases.

Examples of fluororesins include PTFE, PF
A, FEP, ETFE and the like, preferably low molecular weight PTFE having a molecular weight of 1,000,000 or less, PFA, FE
P. These can be used alone or as a mixture.

The resin composition of the present invention may further contain, if necessary, known additives such as an ultraviolet absorber, an antioxidant, a pigment, a molding aid, glass fibers, carbon fibers and the like. The amounts of these additives may be appropriately selected according to the use of the resin composition.

The resin composition of the present invention can be used for OA equipment (for example, housing materials for personal computers, facsimile machines, copiers, printers, etc., chassis materials, CDs, etc.).
-It can be used as a heat-resistant resin used for ROM tray materials, bearing sliding members, paper feeder materials, keyboard materials) or as a material for sliding members. Further, the resin composition of the present invention can also be used as a resin for members requiring slipperiness, abrasion resistance, and heat resistance in home electric appliances (for example, air conditioners, video devices), cameras, automobile parts, and the like.

In addition, by adding a fluoroalkyl-containing polymer (B) having an α-fluoroacrylate having a low surface tension, a resin molded article having excellent water and oil repellency can be obtained. And kitchen utensils, bathroom accessories, toilet utensils (eg, basins, bathtubs,
It can also be used for waste storage. Furthermore, the resin composition of the present invention can also be used as a resin for electronic or electrical connector materials.

The above-mentioned molded article can be produced by molding the resin composition of the present invention. As a molding method, known molding methods such as injection molding, compression molding, transfer molding, extrusion molding, plow molding, and calendar molding can be adopted.

[0021]

EXAMPLES In the following examples, parts are by weight unless otherwise specified. In the examples, tests were performed as follows.

Contact Angle The contact angle of water and n-hexadecane on the surface of the molded product was determined using a contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd.

Synthesis Example 1 2,2,3,3,3-pentafluoropropanol (CF ₃
CF ₂ CH ₂ OH) 300 g (2 mol) and CH ₂ ＣCFC
200 g (1.8 mol) of OF are reacted at 0 ° C. in the presence of 2 mol of triethylamine to give CH ₂ ＣＦCFCOO
355 g (1.6 mol) of CH ₂ CF ₂ CF ₃ were obtained. boiling point:
45 ° C / 62 mmHg.

Synthesis Example 2 300 g of 2,2,3,3,3-pentafluoropropanol
(2 mol) CH ₂ ＣC (CH ₃ ) COCl 188 g
(1.8 mol) at 0 ° C. in the presence of 2 mol of triethylamine to give CH ₂ ＣC (CH ₃ ) COOCH ₂ C
327 g (1.5 mol) of F ₂ CF ₃ were obtained. Boiling point: 52 ° C
/ 60 mmHg).

Synthesis Example 3 C ₃ F ₇ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COF
6 g (0.81 mol) and 25 g (0.66 mol) of LiAlH ₄ were reacted in 500 cc of diethyl ether at 34 ° C., and the resulting reaction mixture was neutralized with 18% hydrochloric acid, and the oil layer was separated. , Distilled, C ₃ F ₇ OCF (CF ₃ ) CF ₂ OC
273.3 g (0.57 mol) of F (CF ₃ ) CH ₂ OH were obtained. Boiling point: 156 ° C / 760 mmHg. 60.7 g (0.66 mol) of the alcohol obtained above and CH ₂ ＣＦCFCOF
Are reacted at 0 ° C. in the presence of 2 mol of triethylamine to give CH ₂ ＣＦCFCOOCH ₂ CF (CF ₃ ) OCF ₂ CF
310 g (0.56 mol) of (CF ₃ ) OC ₃ F ₇ were obtained. Boiling point: 64 ° C / 7 mmHg.

Polymerization Example 1 Using 100 parts by weight of the monomer obtained in Synthesis Example 1, 0.1 part by weight of azobisisobutyronitrile and 0.5 part by weight of n-dodecylmercaptan, bulk polymerization was carried out at 60 ° C. for 3 hours. This was performed to obtain a fluoroacrylic polymer of α-fluoroacrylic acid. The molecular weight of the obtained polymer was measured by gel permeation chromatography (gel permeation chromatography, manufactured by Nippon Waters Limited. Columns: Shodex A-803, A-805, A-80).
6 connected columns. Solvent: acetonitrile. Measurement temperature: 4
0 ° C. It was 220,000 as measured by a standard sample: polystyrene). The thermal decomposition onset temperature measured with a differential thermogravimetric simultaneous analyzer (heating rate: 10 ° C./min, in air) was 349 ° C.

Polymerization Example 2 A copolymer containing α-fluoroacrylic acid fluoroacrylic acid was prepared under the same conditions as in Polymerization Example 1 except that the monomer was replaced with a mixture of 80 parts by weight of the monomer obtained in Synthesis Example 1 and 20 parts by weight of methyl methacrylate. Manufactured. When the molecular weight of the obtained polymer was measured by the same method as in Polymerization Example 1, it was found to be 18
It was 10,000. Differential thermogravimetric simultaneous measurement device (heating rate: 1
(0 ° C./min, in air).
It was 0 ° C.

Polymerization Example 3 Using 100 parts by weight of the monomer obtained in Synthesis Example 2, 0.1 part by weight of azobisisobutyronitrile and 0.5 part by weight of n-dodecylmercaptan, bulk polymerization was carried out at 60 ° C. for 3 hours. A polymer was obtained. When the molecular weight of the obtained polymer was measured by the same method as in Polymerization Example 1, it was 350,000. The thermal decomposition onset temperature measured by a differential thermogravimetric simultaneous measuring device (heating rate: 10 ° C./min, in air) was 252 ° C.

Polymerization Example 4 A mixture of 100 parts by weight of the monomer obtained in Synthesis Example 3 and 1 part by weight of azobisisobutyronitrile was placed in a glass tube.
After sealing under reduced pressure, the mixture was left standing in a constant temperature bath at 60 ° C. for 24 hours to perform bulk polymerization to obtain a fluoroacrylic acid-containing polymer having α-fluoroacrylic acid. The molecular weight of the obtained polymer was measured by gel permeation chromatography (gel permeation chromatography, manufactured by Nippon Waters Limited, column: Dupont trimodal column kit, solvent: hexafluorometa-xylene, measurement temperature:
40 ° C. It was 1.06 million as measured by a standard sample: polystyrene). The pyrolysis temperature measured by a simultaneous thermogravimetric differential analyzer (heating rate: 10 ° C./min, in air) was 301 ° C.

Example 1 Polyphenylene sulfide (PP) was used as a thermoplastic resin.
S) Resin (trade name: T-4, manufactured by Topren Corporation) 100
In a tamper, a powder obtained by blending 5 parts by weight of the α-fluoroacrylic acid fluoroacrylic polymer obtained in Polymerization Example 1 with the powder was preliminarily mixed at room temperature for 10 minutes, and compounded by a twin-screw kneading extruder. The mixture was pelletized to obtain a heat-resistant resin composition. As conditions for kneading and extrusion, an extrusion temperature of 320 ° C., a screw rotation speed of 130 rotations / minute, and a supply amount of 8 kg / hr were employed.

Next, a test piece (disk-shaped molded product having an outer diameter of 4.6 cm, an inner diameter of 1.2 cm, and a thickness of 0.3 cm) was prepared using an injection molding machine (trade name: SG50, manufactured by Sumitomo Heavy Industries, Ltd.). Then, the contact angles of water and n-hexadecane on this test piece were measured. Table 1 shows the results.

Comparative Example 1 The same procedure as in Example 1 was repeated, except that the fluoroacrylic acid α-fluoroacrylate obtained in Polymerization Example 1 was not used. Table 1 shows the results.

Comparative Example 2 The same procedure as in Example 1 was repeated, except that the polymer obtained in Polymerization Example 3 was used instead of the fluoroacrylic polymer of α-fluoroacrylic acid obtained in Polymerization Example 1. Table 1 shows the results
Shown in

Example 2 PPS resin (trade name T-4, manufactured by Topren Co., Ltd.) 10
A powder obtained by blending 0 parts by weight with 5 parts by weight of the α-fluoroacrylic acid-containing fluoroacrylic copolymer obtained in Polymerization Example 2 was preliminarily mixed in a tamper at room temperature for 10 minutes, and a twin-screw kneading extruder was used. By this, the compound was pelletized to obtain a heat-resistant resin composition. As conditions for kneading and extrusion, an extrusion temperature of 320 ° C., a screw rotation speed of 130 rotations / minute, and a supply amount of 8 kg / hr were employed.

Next, a test piece (a disc-shaped molded product having an outer diameter of 4.6 cm, an inner diameter of 1.2 cm, and a thickness of 0.3 cm) was prepared using an injection molding machine (trade name: SG50, manufactured by Sumitomo Heavy Industries, Ltd.). Then, the contact angle of the test piece with water and n-hexadecane was measured. Table 1 shows the results.

Example 3 PPS resin (trade name: T-4, manufactured by Topren Co., Ltd.) 10
A powder obtained by blending 0 parts by weight and 5 parts by weight of the α-fluoroacrylic acid fluoroacrylic polymer obtained in Polymerization Example 4 was preliminarily mixed at room temperature for 10 minutes in a tamper, and was subjected to a twin-screw kneading extruder. The compound was pelletized to obtain a heat-resistant resin composition. As conditions for kneading and extrusion, an extrusion temperature of 320 ° C., a screw rotation speed of 130 rotations / minute, and a supply amount of 8 kg / hr were employed.

Next, a test piece (a disc-shaped molded product having an outer diameter of 4.6 cm, an inner diameter of 1.2 cm, and a thickness of 0.3 cm) was prepared using an injection molding machine (trade name: SG50, manufactured by Sumitomo Heavy Industries, Ltd.). Then, the contact angle of the test piece with water and n-hexadecane was measured. Table 1 shows the results.

Example 4 PPS resin (trade name: T-4, manufactured by Topren Co., Ltd.) 10
0 parts by weight, 5 parts by weight of the α-fluoroacrylic acid fluoroacrylic polymer obtained in Polymerization Example 4, and low molecular weight polytetrafluoroethylene (Lupron L-5, trade name, manufactured by Daikin Industries, Ltd., weight average molecular weight: about 300,000) 30 Parts by weight were mixed in the same manner as in Example 1 to obtain a heat-resistant resin composition. As in Example 1, the contact angle between water and n-hexadecane was measured. Table 1 shows the results.

Comparative Example 3 The same procedure as in Example 4 was repeated except that the polymer obtained in Polymerization Example 4 was not used. Table 1 shows the results.

[0040]

[Table 1]

[0041]

Industrial Applicability The resin composition of the present invention is a thermoplastic resin having a molding temperature of 300 ° C. or higher, which comprises a polymer containing α-fluoroacrylic acid having extremely high heat resistance and excellent water and oil repellency. Obtained by melt-kneading. This resin composition is a very useful molding material that exhibits water and oil repellency without impairing the heat resistance, and even after molding, the α-fluoroacrylic acid-containing fluoroacrylic-containing polymer segregates on the surface, and was expected. The effect is sustained.

Claims (8)

[Claims] 1. A thermoplastic heat-resistant resin (A) having a molding temperature of 300 ° C. or higher, and formula (1): Rf—O—CO—CF ＝ CH ₂ (1) _{, X-R F - (CH} 2) n -, or the formula (2): ## STR2 ## _{R F '- (OCF 2 CF} 2 CF 2) a- (OCF (C
F ₃ ) CF ₂ ) b- (OCF ₂ ) c- (OCF ₂ CF ₂ ) d-OC (Z)
F- (CF ₂ ) e- (where n is 1 or 0; X represents hydrogen or a fluorine atom or a methyl group; R _F has 1 to 2 carbon atoms)
It is a linear or branched perfluoroalkylene group of 0. However, when n is 0 R _F is -C (CF _{3) 2} - shows a. Z represents a fluorine atom or a trifluoromethyl group, and R _F ′ represents a perfluoroalkyl group having 1 to 3 carbon atoms. a, b, c, d and e each independently represent an integer of 0 or 1 or more, a + b + c + d + e is at least 1, and each repetition of a, b, c, d and e The order of the units is not limited in the formula. ). A resin composition comprising a polymer (B) obtained by polymerizing α-fluoroacrylic acid represented by｝ as an essential component. 2. The resin (A) is at least one selected from the group consisting of polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, polyamideimide, polyetherimide, polyetheretherketone and aromatic polyester. The resin composition according to claim 1, which is a resin. 3. The resin composition according to claim 1, wherein the proportion of the resin (B) is 1 to 10% by weight based on the total weight of the resin composition. 4. The resin composition according to claim 1, further comprising a fluororesin. 5. The resin composition according to claim 4, wherein the proportion of the fluororesin is 5 to 40% by weight based on the total weight of the resin composition. 6. The fluorine resin is at least one fluorine selected from the group consisting of polytetrafluoroethylene, tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer and tetrafluoroethylene-hexafluoropropylene copolymer. 5. A resin according to claim 4.
Or the resin composition according to 5. 7. The resin composition according to claim 4, further comprising an additive. 8. A molded article comprising the resin composition according to claim 1.